Azole derivatives of spiroheterocycles

ABSTRACT

A compound having the structural formula ##STR1## 
     where 
     R is C 2  -C 8  alkylene having 2 to 4 carbon atoms linking X and Y; 
     R 1  is C 1  -C 8  linear or branched alkylene, C 1  -C 6  oxyalkylene, C 1  -C 6  thioalkylene or C 1  -C 6  aminoalkylene; 
     R 2  and R 3  are the same or different and are hydrogen, halogen, C 1  -C 8  alkyl, C 1  -C 6  alkoxy, C 1  -C 6  alkylthio, C 1  -C 6  alkylsulfonyl, phenyl substituted phenyl, phenoxy, substituted phenoxy, cyano, nitro, --OCOR 4 , --COOR 5 , --CH m  Q 3-m  or --OCH m  Q 3-m  ; 
     R 4  is C 1  -C 4  alkyl; 
     R 5  is hydrogen or C 1  -C 4  alkyl; 
     Q is halogen; 
     X and Y are the same or different and are oxygen, sulfur, sulfinyl, sulfonyl or if one is NH, the other is sulfur; 
     Z is nitrogen or CH; and 
     m is 1, 2 or 3; 
     and physiologically acceptable salts thereof, 
     is disclosed. A process for synthesizing the compound of this invention is also set forth. This process involves reacting a compound having the structural formula ##STR2## 
     where R 1 , R 2 , R 3  and Z have the meanings given for the compound of this invention with a compound having the structural formula 
     
         HX--R--YH 
    
     where R, X and Y have the meanings given for the compound of the present invention. The compounds of this invention find utility as fungicides and plant growth regulants. Thus, the instant invention is also directed to processes for controlling fungi and regulating plant growth by utilizing effective amounts of the compound of the present invention to effectuate these goals. Finally, fungicidal and plant growth regulant compositions comprising effective amounts of the compound of this invention and carriers therefor is within the contemplation of the present invention.

This is a division of application Ser. No. 07/521,193 filed May 9, 1990,now U.S. Pat. No. 5,106,409, which was a division of application Ser.No. 07/191,932 filed May 9, 1988, now U.S. Pat. No. 4,943,311.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention is directed to a new class of azole derivatives ofspiroheterocycles. More specifically, the present invention is directedto a new class of azole derivatives of spiroheterocycles useful asfungicides and plant growth regulants.

2. Background of the Prior Art

The control of phytopathogenic fungi is of great economic importancesince fungal growth on plants or on parts of plants, i.e., fruits,blossoms, foliage, stems, tubers, roots inhibits production of foliage,fruit or seed and the overall quality of the harvested crop.

Obviously, fungicides are well known in the art. However, the continuouseconomic toll, discussed above, taken by fungi establish a continuingneed to develop new, more effective fungicides which possess curative,preventative and systemic action to protect cultivated plants. Thoserequirements must be accomplished without any adverse side effects,caused by the fungicide, on the plants to be protected.

Another need in the art is the continual requirement to develop new andeffective plant growth regulants. As in the case of fungicides, there isa continuing need in the art to develop new and better plant growthregulants which regulate the growth of plants such that the difficultyand high coast of harvesting economically important plants issignificantly reduced. Especially desirable are plant growth regulantsthat retard undesirable growth, such as excess foliage, of importantcrops without adversely affecting the yield and quality of thecommercial crop to be harvested.

Compounds containing 1,3-dioxolane, 1,3-dithiolane and thiazolidinerings are known in the art. Such compounds are recited to possessspermicida, antimicrobial, anticonvulsant and fungicidal propertiesdepending upon their structure.

Thiazolidine compounds are disclosed in European Patent Application92,158. The compounds of this disclosure are recited to possessfungicidal properties. The thiazolidine compounds of the '158application are structurally distinguished from azole derivatives ofspiroheterocycles.

U.S. Pat. No. 4,402,963 describes a class of dioxolanylalkyltriazolecompounds which are not spiroheterocycles. These compounds are recitedto possess important microbicidal properties. They are also set forth tobe effective in combating phytopathogenic fungi.

U.S. Pat. No. 4,359,475 is directed to a class of thioketal substitutedN-alkyl imidazoles. These compounds, although azole derivatives, are notspiroheterocycles. The compounds of this disclosure are described aspossessing utility as spermicides, as antimicrobials and asanticonvulsant agents.

Fundamentally, the compounds disclosed in the above three references arecharacterized by a following structural formula: ##STR3## Azolederivative of spiroheterocycles have the generic formula as follows:##STR4##

As the two above formulas establish, spiroheterocyclic compounds arecharacterized by a linkage between the 2-position bearing the azolemoiety and the 2'-position of the aryl ring. The prior art disclosuresprovide no such linkage as indicated above.

Other references of interest include European Patent Applications 61,789and 61,794. These two publications disclose the same class of compoundspossessing the same utility, antimicrobial properties. The onlydifference between them is that the former application describestriazole derivatives and the latter application imidazole derivatives.Otherwise, the compounds of these two applications are identical. Thesecompounds are far removed from azole derivatives of spiroheterocycles.It is noted that U.S. Pat. No. 4,483,865 is substantially identical withEuropean Patent Application 61,794.

European Patent Application 29,355 is representative of another class ofimidazole or triazole derivatives having utility as microbicidal agents.These azolyl ketals are not only distinguished from the twoabove-mentioned European patent applications, but are also far removedfrom spiroheterocycles. The only similarity between the compounds ofthis European patent application and the compounds of the presentinvention is that they are said to be effective microbicidal agents,especially in combatting phytopathogenic fungi. U.S. Pat. No. 4,479,004is substantially identical to European Patent Application 29,355.

Still another class of triazole derivatives, useful as an antimicrobialagent, as a fungicide and as a plant-growth regulant,1-(beta-aryl)ethyl-1H-1,2,4-triazole ketals, are set forth in U.S. Pat.No. 4,079,062.

Arch. Pharmaz. (Weinheim, Ger.) 308, 94 (1975) discloses certainsubstituted benzoates, carbamates, and thiocarbamates as well asbenzylic ethers prepared as derivatives of 2-imidazolyl-1-indanol and2-imidazolyl-1-tetralol alcohols and found to be fungicidally active.

Finally, British Patent Application 2,098,607 discloses still anotherclass of triazole or imidazole derivatives useful as agriculturalfungicides as well as possessing antimycotic and/or anticonvulsive andanxiolytic agents in the pharmaceutical field. For example, compoundstaught in this reference are alleged to provide effective control ofparasitic fungi, for treating various forms of epilepsy andpsychological diseases. These compounds are far removed from azolederivatives of spiroheterocycles.

The above remarks establish the need in the art for new and improvedfungicides and plant-growth regulants. The above discussion,furthermore, emphasizes the uniqueness of azole spiroheterocyclecompounds. Such compounds are not only not disclosed in the art, but noteaching of their use as fungicides or plant-growth regulants is made.

BRIEF SUMMARY OF THE INVENTION

The present invention is directed to a new class of azole derivativesproviding excellent fungicidal and plant-growth regulant properties.Their structural uniqueness is based on the fact that the azoles arederivatives of spiroheterocycles. Such compounds are unknown in the artand have never been identified as having utility in the applications setforth herein.

In accordance with the present invention, a new class of compoundshaving the structural formula ##STR5## where R is C₂ -C₈ alkylene having2 to 4 carbon atoms linking X and Y;

R¹ is C₁ -C₈ linear or branched alkylene, C₁ -C₆ oxyalkylene, C₁ -C₆thioalkylene or C₁ -C₆ aminoalkylene;

R² and R³ are the same or different and are hydrogen, halogen, C₁ -C₈alkyl, C₁ -C₆ alkoxy, C₁ -C₆ alkylthio, C₁ -C₆ alkylsulfonyl, phenyl,substituted phenyl, phenoxy, substituted phenoxy, cyano, nitro, --OCOR⁴,--COOR⁵, --CH_(m) Q_(3-m) or --OCH_(m) Q_(3-m) ;

R⁴ is C₁ -C₄ alkyl;

R⁵ is hydrogen or C₁ -C₄ alkyl;

Q is halogen;

X and Y are the same or different and are oxygen, sulfur, sulfinyl,sulfonyl or if one is NH, the other is sulfur;

Z is nitrogen or CH; and

m is 1, 2 or 3;

and physiologically acceptable slats thereof.

In another aspect of the present invention, a process for forming thecompounds of the present invention is taught. In this process, an azoleketone having the structural formula ##STR6## where R¹, R², R³ and Zhave the meanings given above, is reacted with a compound having thestructural formula

    HX--R--YH

where X, Y and R have the meanings given above in the presence of anacid catalyst. An exception is made in the case where the meanings of Xand Y are sulfinyl or sulfonyl. In those cases the spiroheterocyclehaving the structure of formula I following is reacted withm-chloroperoxybenzoic acid in a chlorinated hydrocarbon solvent, i.e.,where X=SO, Y=SO and X=SO₂, Y=SO₂, compounds are prepared by oxidizationof the spiroheterocycles. Also, in those cases where X is NH and Y issulfur the azole ketone compound is reacted with an amino-substitutedreagent or its hydrochloride salt in the presence of a base catalyst.

In still another aspect of the instant invention, a process is providedfor controlling fungi. In this process, a fungicidally effective amountof the compound of the present invention is applied to the locus to beprotected.

In yet another aspect of the present invention, a fungicidal compositionis disclosed. The fungicidal composition includes a fungicidallyeffective amount of the compound of the present invention and a carriertherefor.

In still yet another aspect of this invention, a process for controllingplant growth is set forth. In this process a plant growth regulanteffective amount of the compound of the present invention is applied tothe plant to be regulated.

In a final aspect of the subject invention, a plant growth compositionis described. The plant growth composition of the present inventioncomprises a plant growth effective amount of the compound of the presentinvention and a carrier therefor.

DETAILED DESCRIPTION OF THE INVENTION

The compound of the instant invention has the following structuralformula ##STR7## where R is C₂ -C₈ alkylene having 2 to 4 carbon atomslinking X and Y;

R¹ is C₁ -C₈ linear or branched alkylene, C₁ -C₆ oxyalkylene, C₁ -C₆thioalkylene or C₁ -C₆ aminoalkylene;

R² and R³ are the same or different and are hydrogen, halogen, C₁ -C₈alkyl, C₁ -C₆ alkoxy, C₁ -C₆ alkylthio, C₁ -C₆ alkylsulfonyl phenylsubstituted phenyl, phenoxy, substituted phenoxy, cyano, nitro, --OCOR⁴,--COOR⁵, --CH_(m) Q_(3-m) or --OCH_(m) Q_(3-m) ;

R⁴ is C₁ -C₄ alkyl;

R⁵ is hydrogen or C₁ -C₄ alkyl;

Q is halogen;

X and Y are the same or different and are oxygen, sulfur, sulfinyl,sulfonyl or if one is NH, the other is sulfur;

Z is nitrogen or CH; and

m is 1, 2 or 3;

and physiologically acceptable salts thereof.

More preferably, the compound of the present invention has thestructural formula (I) where

R is --(CH₂)_(n) --, --CH₂ CH(R⁶)-- or --CH(CH₃)--CH(CH₃)--;

R¹ is C₁ -C₃ alkylene, C₁ -C₃ oxyalkylene or C₁ -C₃ thioalkylene;

R² and R³ are the same or different and are hydrogen, halogen, C₁ -C₄alkyl, C₁ -C₄ alkoxy, C₁ -C₄ alkylthio, C₁ -C₄ alkylsulfonyl, phenyl,substituted phenyl, phenoxy, substituted phenoxy, cyano, or nitro;

R⁶ is C₁ -C₆ alkyl;

X and Y are the same or different and are oxygen, sulfur, sulfinyl,sulfonyl or if one is NH, then the other is sulfur;

Z is nitrogen or CH; and

n is 2 or 3;

and physiologically acceptable salts thereof.

The present invention is also directed to a process for the formation ofa compound whose structural formula is (I). In one embodiment of theprocess of forming the compound having structural formula (I), acompound having the structural formula ##STR8## where R¹, R², R³ and Zhave the meanings given for the compound having structural formula (I)is reacted with a compound having the structural formula

    HX--R--YH                                                  (III)

where

R has the meanings given for structural formula (I); and

X and Y are the same or different and are oxygen or sulfur.

In this preferred embodiment, the compounds having the structuralformulas (II) and (III) are reacted in the presence of an acid catalyst.Preferably, the acid catalyst is p-toluenesulfonic acid ormethanesulfonic acid. In the preferred embodiment wherein the compound(III) is a dithiol (where X and Y are both sulfur) the reaction ispreferably carried out neat in methanesulfonic acid. In anotherembodiment, the reaction occurs in the presence of a solvent mixture. Inthis embodiment, the preferred solvent mixture is a mixture of tolueneand n-butanol.

In a second preferred embodiment, the process for synthesizing thecompound having the structural formula (I) involves reacting a compoundhaving the structural formula (II), where R¹, R², R³ and Z have themeanings given for structural formula (I), with the compound having thestructural formula (III) where one of X and Y is NH and the othersulfur. In this embodiment, the compound (III), the amino substitutedcompound or its hydrochloride salt, is reacted in the presence of a basecatalyst. Preferably, the base catalyst is a trialkylamine, withtriethylamine particularly preferred.

In yet a third preferred embodiment of the process of forming thecompound having the structural formula (I), where X and Y are the sameand are sulfinyl or sulfonyl, a compound having the structural formula(II), where R¹, R², R³ and Z have the meanings given for the compoundhaving the structural formula (I), is reacted with a compound having thestructural formula (III), where X and Y are sulfur, in the presence ofan acid catalyst. The preferred acid catalyst in this reaction ismethanesulfonic acid. This results in the formation of a compound havingthe structural formula (I) where X and Y are sulfur.

This compound is then oxidized by reaction with m-chloroperoxybenzoicacid in a chlorinated hydrocarbon solvent, preferably dichloromethane orchloroform. To obtain the sulfinyl compound, two equivalents ofm-chloroperoxy-benzoic acid are reacted per equivalent of compound (I)where X and Y are sulfur. That is, the molar ratio of compound (I) tom-chloroperoxybenzoic acid is 1:2. The temperature of this reaction ismoderate, in the range of between about 0° C. and ambient temperature.

In order to synthesize the sulfonyl compound having the structuralformula (I), the oxidation reaction of the compound having thestructural formula (I) where X and Y are sulfur withm-chloroperoxybenzoic acid involves a molar ratio ofm-chloroperoxybenzoic acid to compound (I) of at least 4:1. That is, atleast 4 equivalents of m-chloroperoxybenzoic acid are used perequivalent of compound (I). More preferably, more than 4 equivalents ofthe m-chloroperoxybenzoic acid are reacted per equivalent of compound(I). The temperature of this reaction is the reflux temperature of thechlorinated hydrocarbon solvent in which this oxidation reaction occurs.

Those skilled in the art will be aware that the compounds of the presentinvention, made in accordance with the processes discussed immediatelyabove, contain asymmetric carbon atoms. This is illustrated in formula(IV) below which depicts the compound of the present inventioncontaining asymmetric carbon atoms at positions 2 of thespiroheterocyclic ring and at the 2'-position of the fused bicyclicring. ##STR9##

In addition, another asymetric carbon atom exists at either the4-position or 5-position of the spiroheterocyclic ring. This isillustrated in structural formula (V) below wherein R⁷ and R⁸ can beindividually C₁ -C₆ alkyl. ##STR10##

Stereoisomers depicted in structural formulas (IV) and (V) may or maynot be separated. It is emphasized that not only are the separateisomers within the scope of the present invention, but mixtures of twoor more of the stereoisomers, which may not necessarily be separated,are also within the scope of the present invention.

The triazole ketones having the structural formula (II) are generallynovel. The triazole ketones having the structural formula (II) areprepared by the reaction of a haloketone having the structural formula##STR11## wherein R¹, R² and R³ have the meanings given for the compoundhaving the structural formula (I) and X¹ is chlorine or bromine, with anazole compound having the structural formula ##STR12## This method isanalogous to that disclosed in P. A. J. Janssen et al, J. Med. Chem.1969, 12, 784 whose disclosure is incorporated herein by reference.

In the case where R¹ is an alkylene containing an oxygen atom, byanalogy, an alternate method of preparing triazole ketones having thestructural formula (VII) is set forth in J. Heterocyclic Chem., 21, 311(1984) wherein the preparation of imidazole ketones is disclosed. Thisdisclosure is also incorporated herein by reference.

The haloketones defined by structural formula (VI) are generally knownand may be prepared by known methods.

The compounds having the structural formula (I) are useful in a processfor controlling phytopathogenic fungi. In this process a fungicidallyeffective amount of the compound having structural formula (I) where themeanings of R, R¹, R₂, R³, R⁴, R⁵, R⁶, Q, X, Y, Z, m and n are thosegiven for the compound of structural formula (I) is applied to the locusunder attack by said fungi.

In a first preferred embodiment, the method by which a fungicidallyeffective amount of the compound having structural formula (I) isapplied to the plants to be protected from phytopathogenic fungi is byapplication of the compound having the structural formula (I) to thefoliage of the plants to be protected. This compound is applied to thefoliage in a concentration of 0.125 to 10 kilograms per hectare (kg/ha).More preferably, the embodiment wherein fungi are controlled in aprocess comprising applying a fungicidally effective amount of thecompound having structural formula (I) entails applying 0.125 to 5.0kg/ha of compound (I) to the foliage of the plants to be protected fromsaid phytopathogenic fungi.

In the second preferred embodiment of the process for controllingphytopathogenic fungi, a fungicidally effective amount of the compoundhaving the structural formula (I) is applied to the soil in which theplants to be protected from phytopathogenic fungi are grown. In thisembodiment, the compound having the structural formula (I) is applied tothe soil in which the plants to be protected are grown at aconcentration of 10 to 500 mg/l. The exact dosage, within thisconcentration range, is dictated by the fungi to be controlled and theparticular plants to be protected.

As those skilled in the art are aware, the first preferred embodiment ofthe process for controlling fungi is the foliage method. The secondpreferred embodiment is the systemic method of application. Eithermethod may be utilized prior to infection or after fungi attack hasbegun.

Alternately, in yet another embodiment of the process of the presentinvention for controlling phytopathogenic fungi, the compound having thestructural formula (I) may be applied to the seeds as a coating. Thismethod provides plant protection from dangerous fungi by eitherchemotherapeutic means or systemic means or both. That is, the coatingto the seed may protect the soil from infection by the fungi or may betaken up by the plant systemically to protect the plant from the fungalattack. In this seed coating method, the appropriate concentration ofthe compound having the structural formula (I) is in the range ofbetween 5 and 75 grams of compound per 100 kg. of seed.

In still another aspect of the present invention, a process forregulating growth of a plant is provided. In this process a plant growthregulant effective amount of the compound having structural formula (I),where R, R¹, R₂, R³, R⁴, R⁵, R⁶, R⁷, R⁸, Q, X, Y, Z, m and n have themeanings given for compounds (I), is applied to the plant whose growthis to be regulated.

Yet another important aspect of the present invention involves thedisclosure of new fungicidal compositions. The fungicidal composition ofthe present invention comprises a fungicidally effective amount of thecompound having the structural formula (I), where R, R¹, R₂, R³, R⁴, R⁵,R⁶, R⁷, R⁸, Q, X, Y, Z, m and n have the meanings given for compound(I), and a carrier therefor.

More preferably, the fungicidal composition comprises a fungicidallyeffective amount of the compound having structural formula (I), whereinthe meanings of R, R¹, R₂, R³, R⁴, R⁵, R⁶, R⁷, R⁸, X, Y, Z, m and n havethe preferred meanings for the compound having structural formula (I),and a carrier therefor.

In a final aspect of the present application a plant growth regulantcomposition is provided. This composition comprises a plant growthregulant effective amount of the compound having the structural formula(I), where R, R¹, R₂, R³, R⁴, R⁵, R⁶, R⁷, R⁸, Q, X, Y, Z, m and n havethe meanings given for compound (I), and a carrier therefor.

More preferably, a plant growth regulant composition is disclosed whichcomprises a plant growth regulant effective amount of the compoundhaving structural formula (I) wherein the preferred meanings of R, R¹,R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, X, Y, Z, m and n are those given for thepreferred embodiment of the compound having structural formula (I), anda carrier therefor.

The carrier employed in the fungicidal and plant growth regulantcompositions may be a finely divided or granular organic or inorganicinert material. Among the inert carriers within the contemplation ofthis invention are attapulgate clay, sand, vermiculite, corncobs,activated carbon and mineral silicates such as mica, talc, pyrophylliteand clays.

In another preferred embodiment of carrier employed in the compositionof this invention, the carrier comprises a solution. That is, the activeagent, a compound whose structural formula is (I) is dissolved in asuitable solvent which acts as the carrier. Among the solvents, actingas carrier, within the contemplation of this invention are acetone,methanol, isopropanol, t-butyl alcohol, cyclohexanol, n-butyl alcohol,cyclohexanone, toluene, xylene, dioxane, dimethylformamide,dimethylsulfoxide, ethylene dichloride, diacetone alcohol, andN-methylpyrrolidone.

In still another preferred embodiment of the carrier utilized in thecomposition of the present invention, the carrier comprises a wateremulsion. The water emulsion is prepared from a solution as describedimmediately above. To the solution is added a surface active agent.Surface active agents suitable for use in forming the emulsion of thisinvention are known to those skilled in the art. McCutcheon's Detergentsand Emulsifiers, Allured Publishing Corp., Ridgewood, N.J. (1970); U.S.Pat. No. 2,514,916, Columns 2 to 4; and U.S. Pat. No. 2,547,734, Columns3 and 4, provide detailed examples of such surface active agents. Thesurface active agents may be anionic, non-ionic or cationic.

In still another embodiment of a carrier used in the composition of thepresent invention, the carrier is a dispersant. In this embodiment, theactive agent, the compound having structural formula (I), is mixed witha dispersant. The dispersant includes a solvent of the type describedabove, one of the above-described surface active agents and water. Theactive agent is dissolved in the solvent to form a solution. The solventis dispersed in the water with the aid of the surface active agent.

In still another embodiment of the carrier constituent of thecomposition of the present invention, the active compound, the compoundhaving the structural formula (I), is premixed with an inert solidcarrier which is added to a surface active agent and water to provideanother form of dispersion type carrier within the contemplation of thecomposition of this invention.

The embodiment discussed immediately above, the disposal of the compoundhaving the structural formula (I) on a solid inert carrier which isdispersed in the liquid to form a dispersion, may alternatively beemployed in a non-liquid form. That is, the composition of thisinvention may take the form of dust, granules or a paste of a wettablepowder. In these embodiments the active compound of this invention, thecompound having the structural formula (I), is admixed with an inertsolid carrier to form a solid composition. Thus, for example, in theembodiment wherein a powder is formed, the solid inert carrier isprovided in powder form. In many such cases the inert carrier is amineral silicate. The solid may be made wettable by the addition of asurface active agent, well known to those skilled in the art, andreferred to in the above-recited references directed to surface activeagents.

In a final embodiment of the carrier component of the composition ofthis invention, the carrier is an aerosol. To prepare an aerosol, theactive compound is dissolved in a first solvent. This first solvent isconventional in the sense that although it is volatile it is not highlyvolatile. This solution is then admixed with a highly volatile solvent,a so-called liquid aerosol carrier. The aerosol carrier is liquid onlyunder elevated pressure. At ordinary temperatures and at atmosphericpressure, the aerosol carrier is a gas. In a subembodiment of thispreferred carrier, the aerosol carrier may itself be active. Forexample, the carrier may be an insecticide, a herbicide, a bactericideor the like.

Among the carriers discussed above, the carriers comprising solvents andemulsions are particularly preferred in the production of the fungicidaland plant growth regulant compositions of the present invention.

The following examples are given to illustrate the scope of the presentinvention. Because these examples are given for illustrative purposesonly, the invention embodied herein should not be limited to the actualexamples provided.

EXAMPLE 1 Preparation of3',4'-Dihydro-2'-(1H-1,2,4-Triazol-1-yl)-Spiro-[1,3-Dioxolane-2,1'(2'H)-Naphthalene](CompoundNo. 35)

A mixture of 10 g.3,4-dihydro-2-(1H-1,2,4-triazol-1-yl)-1-(2H)-naphthalenone, 5.8 g.ethylene glycol and 11.5 g. p-toluenesulfonic acid was refluxed in amixed solvent of 150 ml. toluene and 70 ml. n-butanol under a Dean-Stark[trademark] trap for 48 hours. The solvent was evaporated leaving aslurry which was taken up in dichloromethane and washed twice with 10%aqueous sodium hydroxide and once with water. The extract was dried insodium sulfate, filtered and evaporated leaving an oily residue whichcrystallized on cooling to yield 1.5 g of white crystals. These whitecrystals were3',4'-dihydro-2'-(1H-1,2,4-triazole-1-yl)-spiro-[1,3-dioxolane-2,1'(2'H)-naphthalene].This compound had a melting point of 108° C.

EXAMPLE 2 Preparation of7'-Chloro-3',4'-Dihydro-2-(1H-1,2,4-Triazol-1-yl)-Spiro-[1,3-Dithiolane-2,1'-(2'H)-Naphthalene](Compound No. 48)

To a stirred mixture of 2.7 g.7-chloro-3,4-dihydro-2-(1H-1,2,4-triazol-1-yl)-1 (2H)-naphthalenone and10 ml. methanesulfonic acid at ambient temperature was added 5 ml.ethanedithiol and the resulting mixture was allowed to react overnight.The reaction mixture was diluted with dichloromethane, neutralized withsolid sodium bicarbonate and then washed thoroughly with 20% aqueoussodium hydroxide and water. The organic layer was dried over magnesiumsulfate, filtered and evaporated to yield an oily residue.

The oily residue upon trituration with ethyl ether gave 1.2 g. of7'-chloro-3',4'-dihydro-2-(1H-1,2,4-triazol-1-yl)-spiro-[1,3-dithiolane-2,1'-(2'H)-naphthalene].This compound appeared as white crystals having a melting point of 156°C.-157° C.

EXAMPLE 3 Preparation of2',3'-Dihydro-3'-(1H-Imidazol-1-yl)-Spiro-[1,3-Dithiane-2',4'(4H)-1-Benzopyran](Compound No. 38)

In a manner analogous with Example 2, 4.3 g. of2,3-dihydro-3-(1H-imidazol-1-yl)-4H-1-benzopyran-4-one was reacted with9.2 g. of 1,3-propanedithiol in 20 ml. of methanesulfonic acid to yield2.5 g of white crystals.

The compound,2',3'-dihydro-3'-(1H-imidazol-1-yl-spiro-[1,3-dithiane-2',4'(4H)-1-benzopyran],had a melting point of 146°C.-148° C.

EXAMPLE 4 Preparation of2',3'-Dihydro-2'-(1H-1,2,4-Triazol-1-yl)-Spiro-[Thiazolidine-2,1'(1H)-Indene](Compound No. 46)

To a slurry of 6.3 g.2,3-dihydro-2-(1H-1,2,4-thiazol-1-yl)-1H-inden-1-one in 75 ml. tolueneand 75 ml. n-butanol was added 7.2 g. 2-aminoethanethiol hydrochlorideand 6.4 g. triethylamine. The mixture was refluxed under a Dean-Stark[trademark] trap for 50 hours. After cooling, the formed precipitate wasremoved by filtration and the filtrate was washed with water, dried withsodium sulfate and concentrated to yield an oil. The oil waschromatographed on silica gel and eluted with ethyl acetate. This yield2.1 g. of white crystals. This material, having a melting point of114°-117° C., was identified as2',4'-dihydro-2'-(1H-1,2,4-triazol-1-yl)-spiro-[thiazoladine-2-]'(1H)-indene].

EXAMPLE 5 Preparation of3',4'-Dihydro-2'-(1H-1,2,4-Triazol-1-yl)-Spiro-[1,3-Dithiane-2,1'(2'H-Naphthalene],1,3-Dioxide (Compound No. 21)

To a solution of 3 g.3',4'-dihydro-2'-(1H-1,2,4-triazol-1-yl)-spiro-[1,3-dithiane-2,1'(2'H)-naphthalene]in 100 ml. dichloromethane at 0° C. was added, dropwise, 4 g. of 80-85%m-chloroperoxybenzoic acid in 50 ml. dichloromethane. After the additionwas complete, the mixture was allowed to warm to room temperature andwas stirred overnight. The solution was washed twice with 5% aqueoussodium bicarbonate and once with water. The organic extract was driedover sodium sulfate and evaporated to yield 2.6 g. of white crystals.

These crystals were identified as3',4'-dihydro-2'-(1H-1,2,4-triazol-1-yl)-spiro-[1,3-dithiane-2,1'(2'H-naphthalene),1,3-dioxide], having a melting point of 95° C.-103° C.

EXAMPLE 6 Preparation of3',4'-Dihydro-2'-(1H-1,2,4-Triazol-1-yl)-Spiro-[1,3-Dithiolane-2,1'(2'H)-Naphthalene,1,1,3,3-Tetroxide] (Compound No. 15)

A solution was prepared by adding 100 ml. dichloromethane to 3 g.3',4'-dihydro-2'-(1H-1,2,4-triazol-1-yl)-spiro-[1,3-dithiolane-2,1'(2'H)-naphthalene].Dropwise, 8.9 g. of 80-85% m-chloroperoxybenzoic acid in 100 ml.dichloromethane was added to this solution at room temperature. Afterthe addition was completed, the mixture was refluxed for five hours. Thereaction mixture was then washed twice with 10% aqueous sodiumbicarbonate, once with water, dried with sodium sulfate and evaporatedto yield 2.5 g. of product.

The product,3',4'-dihydro-2'-(1H-1,2,4-triazol-1-yl)-spiro-[1,3-dithiolane-2,1'(2'H)-napthalene],1,1,3,3-tetroxide, had a melting point of 225° C.-226° C. (decomposed).

EXAMPLE 7 Preparation of Compound Nos. 1-14, 16-20, 22-34, 36, 37, 39-45and 47

Compound Nos. 1-14, 16-20, 22-34, 36, 37, 39-45 and 47 were prepared inaccordance with the procedures enumerated in Examples 1 to 6. Thesecompounds are tabulated in Table I. Table I defines the compounds andcharacterizes them by their melting point. Compounds 35, 48, 38, 46, 21and 15, prepared in accordance with the procedures of Examples 1 to 6,respectively, are included in the table for completeness.

Compound Nos. 7, 9, 10, 25 and 42-44 are oils at ambient conditions.These compounds, which cannot be characterized by melting point, werecharacterized by nuclear magnetic resonance (NMR) data. This NMR data isincluded in Table II which follows Table I.

EXAMPLE 8 Preparation of3,4-Dihydro-2-(1H-1,2,4-triazole-1-yl)-1(2H)-Naphthalenone

To a mixture of 30 g. potassium carbonate, 15 g. 1,2,4-triazole and 250ml acetonitrile at 40° C. was added a solution of 45 g.3,4-dihydro-2-bromo-1(2H)-naphthalenone in 150 ml acetonitrile. Themixture was allowed to react for 5 hours at 40° C. and than at refluxtemperature for 2 hours. The solid was removed by filtration and thefiltrate concentrated to dryness leaving a solid residue. This wasdissolved in dichloromethane and washed twice with water. The organicextract was dried over sodium sulfate and evaporated to give 42 grams ofproduct having a melting point of 96°-98° C.

The above procedure is generally applicable to the synthesis of allazole ketones of structural formula (II) with R¹, R², R³ and Z asdefined herein.

                                      TABLE I                                     __________________________________________________________________________     ##STR13##                                                                    Cpd.                                      m.p.,                               No.    X  Y  R         R.sup.1  R.sup.2                                                                            R.sup.3                                                                         Z  °C.                          __________________________________________________________________________    1      S  S  CH.sub.2 CH.sub.2                                                                       CH.sub.2 H    H N  90                                  2      SO.sub.2                                                                         SO.sub.2                                                                         "         "        "    " "  184-90                              3      S  S  (CH.sub.2).sub.3                                                                        "        "    " "  126-8                               4      S  S  "         "        "    " "  197-9                                                                         (CH.sub.3 C.sub.6 H.sub.4                                                     SO.sub.3 H)                         5      SO.sub.2                                                                         SO.sub.2                                                                         "         "        "    " "  295-7                               6      S  S  CH.sub.2 C(CH.sub.3)H                                                                   "        "    " "  185-8(HCl)                          7      S  S  CH.sub.2 C(C.sub.2 H.sub.5)H                                                            "        "    " "  oil*                                8      S  S  CH.sub.2 CH.sub.2                                                                       "        "    " CH 124-5                               9      S  S  CH.sub.2 C(CH.sub.3)H                                                                   "        "    " "  oil*                                10     S  S  CH.sub.2 C(C.sub.2 H.sub.5)H                                                            "        "    " "  oil*                                11     S  S  (CH.sub.2).sub.3                                                                        "        "    " "  100-3                               12     S  S  CH.sub.2 CH.sub.2                                                                       CH.sub.2 CH.sub.2                                                                      "    " N  98-9                                13     S  S  "         "        "    " "  105-6                                                                         (HNO.sub.3)                         14     SO SO "         "        "    " "  172-4                               15     SO.sub.2                                                                         SO.sub.2                                                                         CH.sub.2 CH.sub.2                                                                       CH.sub.2 CH.sub.2                                                                      H    H N  225-6                               16     SO.sub.2                                                                         SO.sub.2                                                                         "         "        "    " "  223-6                                                                         (CH.sub.5 C.sub.6 H.sub.4                                                     SO.sub.3 H)                         17     S  S  "         "        5-OCH.sub.3                                                                        " "  137-9                               18     S  S  "         "        6-OCH.sub.3                                                                        " "  135-40                              19     S  S  "         "        7-OCH.sub.3                                                                        " "  112-4                               20     S  S  (CH.sub.2).sub.3                                                                        "        H    " "  74-78                               21     SO SO "         "        "    " "  95-103                              22     SO.sub.2                                                                         SO.sub.2                                                                         "         "        "    " "  265-7                               23     S  S  CH.sub.2 C(CH.sub.3)H                                                                   "        "    " "  146-54                              24     S  S  CH.sub.2 C(C.sub.2 H.sub.5)H                                                            "        "    " "  113-4                               25     S  S  CH.sub.2 C(C.sub.2 H.sub.5)H                                                            "        "    " "  oil*                                             (isomers)                                                        26     S  S  CH.sub.2 CH.sub.2                                                                       "        "    " CH 158-60                              27     S  S  CH.sub.2 C(CH.sub.3)H                                                                   "        "    " "  103-5                               28     S  S  (CH.sub.2).sub.3                                                                        "        "    " "  141-2                               29     SO SO (CH.sub.2).sub.3                                                                        "        "    " "  100-5                               30     S  S  CH.sub.2 CH.sub.2                                                                       (CH.sub.2).sub.3                                                                       "    " N  95-7                                31     S  S  (CH.sub.2).sub.3                                                                        "        "    " "  132-4                               32     S  S  CH.sub.2 CH.sub.2                                                                       (CH.sub.2).sub.3                                                                       H    H CH 130-3                               33     S  NH CH.sub.2 CH.sub.2                                                                       CH.sub.2 "    " "  162-7                               Isomer B 34                                                                          S  NH "         CH.sub.2 CH.sub.2                                                                      "    " N  99-101                              35     O  O  "         "        "    " "  108                                 36     S  S  "         OCH.sub.2                                                                              "    " CH 127-9                               37     SO SO "         "        "    " "  93-5                                38     S  S  (CH.sub.2).sub.3                                                                        "        "    " "  146-8                               39     S  S  CH.sub.2 CH.sub.2                                                                       OC(CH.sub.3)H                                                                          "    " "  161-3                               40     SO SO "         "        "    " "  143-6                               Isomer A 41                                                                          S  NH "         CH.sub.2 CH.sub.2                                                                      "    " N  120                                 Isomer B 42                                                                          S  S  CH.sub.2 C(C.sub.2 H.sub.5)H                                                            OCH.sub.2                                                                              "    " CH oil*                                Isomer B 43                                                                          S  S  "         "        "    " "  oil*                                Mixture 44                                                                           S  S  CH.sub.2 C(CH.sub.3)H                                                                   "        "    " "  oil*                                Mixture 45                                                                           S  NH CH.sub.2 CH.sub.2                                                                       CH.sub.2 CH.sub.2                                                                      "    " "  105-112                             Mixture 46                                                                           S  NH "         CH.sub.2 "    " N  114-117                             47     S  NH "         OCH.sub.2                                                                              "    " CH 155-158                             48     S  S  "         CH.sub.2 CH.sub.2                                                                      7-Cl " N  156-157                             __________________________________________________________________________     *See Nuclear Magnetic Resonance (NMR) data in Table II.                  

TABLE II Nuclear Magnetic Resonance (NMR) Data

Cpd. No. 7 (CDCl₃): δ8.2 (H,s), 7.9 (1H,s), 7.2-7.8 (4H,m), 5.1-5.4(1H,m), 3.7-4.3 (1H,m), 2.2-3.7 (4H,m), 1.4-2.0 (2H,m), 0.6-1.2 (3H,m)

Cpd. No. 9 (CDCl₃): δ6.8-7.8 (7H,m), 4.7-5.0 (1H, broad t), 3.6-4.3(H,m), 2.2-3.2 (4H,m), 1.0-1.4 (3H,m)

Cpd. No. 10 (CDCl₃): δ6.9-8.0 (7H,m), 4.7-5.0 (1H, broad t), 2.3-4.3(5H,m), 1.4-2.3 (2H,m), 0.7-1.3 (3H, 2 sets of t)

Cpd. No. 25 (CDCl₃): δ8.4 (1H, sxs), 8.3 (1H, sxs), 7.9-8.3 (1H,m),6.9-7.4 (3H,m), 4.7-5.1 (1H,m), 3.8-4.3 (1H,m), 2.3-3.4 (6H,m), 1.4-2.1(2H,m), 0.8-1.2 (3H,m)

Cpd. No. 42 (CDCl₃): δ7.65-8.10 (2H,m), 6.75-7.30 (5H,m), 4.45-4.85(3H,m), 2.90-4.30 (3H,m), 0.80-2.20 (5H,m)

Cpd. No. 43 (CDCl₃): δ7.70-8.10 (2H,m), 4.50-4.80 (3H,m), 2.80-4.25(3H,m), 0.75-2.0 (5H,m)

Cpd. No. 44 (CDCl₃): δ7.67-8.10 (2H,m), 6.70-7.40 (5H,m), 4.50-4.85(3H,m), 2.20-3.30 (3H,m), 1.20-1.50 (3H,m)

EXAMPLE 9 Preparation of Fungicidal and Plant Regulant Compositions

The compounds prepared in Examples 1-7 (Compound Nos. 1-48) were formedinto compositions. This was accomplished by dissolving 0.3 g. of each ofthe compounds in 10 ml. of acetone or other suitable solvent. Each ofthese solutions were treated with 1 to 2 drops of an emulsifying agent,such as Triton [trademark] X-100, and water was added to form anemulsion. The degree of dilution with water dictated by the desiredconcentration of the composition. The greater the quantity of wateradded the lower the concentration of the composition, reported inmilligrams per liter (mg/l).

EXAMPLE 10 Control of Powdery Mildew Fungus (Systemic Root Uptake)

Each of the compounds prepared in accordance with Examples 1-7, CompoundNos. 1-48, were tested to evaluate their effectiveness in preventing orcontrolling powdery mildew disease of barley caused by the fungusErysiphe graminis and powdery mildew disease of cucumber caused by thefungus, Erysiphe cichoracearum. This prevention or control capabilitywas tested by utilizing the compounds of the present invention tocontrol these diseases by systemic root uptake.

To accomplish this task, pots (4×4×3.5 inches) containing 10 plants ofbarley (Variety "Herta") and cucumber (Variety "Marketmore 70") weregrown to age 6 days and 10 days, respectively. Upon reaching these ages,45 ml. of emulsion compositions formed in accordance with Example 9 wereadded to each pot. That is, 48 pots were treated with emulsioncompositions of the 48 compounds prepared in accordance with Examples 1to 7. The 45 ml. compositions saturated the soil without significantloss through drainage into the saucers below the pots. In addition, anumber of pots containing the same barley and cucumber plants were leftuntreated. These pots were used as controls.

Twenty-four hours after the treatment with the compositions of thepresent invention, both the barley and cucumber plants in all the pots,these treated and those untreated, were inoculated with powdery mildewfungus. This was accomplished by tapping leaves of previously infectedbarley and cucumber plants over the treated and untreated potscontaining the barley and cucumber plants, respectively, to distributespores of the fungus over the plants tested.

Six days after inoculation, disease control was evaluated on a 0 to 6rating scale. A 0 rating was assigned when no disease was evidenced anda 6 rating was given for severe disease. Intermediate ratings wereassigned depending on the degree of disease. Percent control wascomputed by comparing the ratings for the treated and untreated plants.

The results of this example, that is, the percent control for each ofthe compounds tested is reported in Table III. The results of thepowdery mildew disease control of barley is reported under the title"BMS 250". The control of cucumber powdery mildew is similarly reportedunder the title of "CMS 250." It is noted that Table III appears afterExample 16.

EXAMPLE 11 Control of Powdery Mildew in Barley by Foliar Application

Eight plants of "Larker" variety barley were planted in a pot. Thenumber of pots were sufficient to accommodate testing in duplicate ortriplicate pots for each of the 48 compounds tabulated in Table I. Thisnumber included a duplicate number of pots which acted as controls aswill be discussed below.

Each of the compounds tabulated in Table 1 were tested by being sprayedonto the plants as compositions, prepared in accordance with Example 9,at a emulsion composition concentration of 1,000 mg/l. Compositions ofeach compound were sprayed on two or three pots. A number of pots wereunsprayed and thus acted as controls. That is, for each pot sprayed anunsprayed pot was utilized as a control.

After the leaves of the sprayed pots were dried, they and the unsprayedcontrol pots were placed in a greenhouse maintained at 21° C. All thepots were then inoculated with barley powdery mildew fungus, Erysiphegraminis. This inoculation was accomplished by distributing spores ofthe fungus over the leaves to be tested from plants which had previouslybeen infected with the mildew disease.

Five days after inoculation, the plants were evaluated and assigned adisease rating of 0 to 6 as described in Example 10. Again, percentcontrol was computed by comparing the treatment scores with the scoresof the untreated controls. The results of these tests are summarized inTable III under the title "BMP 1000."

EXAMPLE 12 Control of Rice Blast Disease by Foliar Treatment

Five Bellemont rice plants were grown in a plurality of pots. The numberof pots with planted rice plants were sufficient to test thecompositions of all 48 compounds listed in Table I as well as controlstherefor, the number of controls equal to the number of pots treatedwith each compound.

Three to four weeks after planting, the rice plants were sprayed withcompositions of the compounds of this invention, prepared in accordancewith Example 9. The concentration of each composition was 1,000 mg/l. Anequal number of pots, also containing five rice plants per pot, remainedunsprayed.

Sprayed and unsprayed pots of the plant were inoculated with spores ofthe rice blast fungus, Pyricularia oryzae. This inoculation wasaccomplished by preparing inoculum containing 20,000 to 30,000 sporesper millilitre. The inoculum so prepared was sprayed on the plants with1 to 2 drops of Tween [trademark] 20 surfactant (exthoxylated sorbitanmonolaurate) to insure proper wetting of the inoculum onto the plantleaves.

The plants were incubated in a controlled chamber at a humidity of 99%and a temperature of 21° C. for about 24 hours to allow infection tooccur. The plants, after 24 hours in the control chamber, weretransferred to a greenhouse for six days to permit disease developmentto occur. Disease was manifested by blast lesions on the leaves. Diseasecontrol was calculated by either counting lesions, if infection wasmoderate, or evaluating by the 0 to 6 rating system defined in Example10. Of course, the evaluation system used in rating any of the compoundsof the present invention was also utilized in evaluating its control.The results of this test are also tabulated in Table III under the title"RCB 1000."

EXAMPLE 13 Control Bean Rust Fungus Eradicant Test

Pots were planted with two pinto bean plants, P. vulgaris each,susceptible to rust disease. When the plants were 7 days old, at theprimary leaf stage of growth, they were all sprayed with a suspensioncontaining 20,000 spores of the bean rust fungus, Uromyces phaseoli, perml. All the pots containing the plants were than incubated in acontrolled environmental chamber, maintained at 99% humidity and 21° C.,for 24 hours to allow infection to occur. The plants were then removedfrom the incubator and allowed to dry. Two days after inoculation theinfected plants were sprayed with compositions formed from the compoundsof this invention, set forth in Example 9, at a dosage of 1,000 mg/l. Anumber of infected plants were not sprayed and acted as controls. All ofthe sprayed and unsprayed plants were then placed in a greenhouse at 21°C. for five days to allow any disease present to be expressed.

All the plants sprayed with the spore suspension were assessed fordisease using the 0 to 6 rating system described in Example 10. Controlof disease was determined by comparing treated plants with the untreatedcontrols. The control of disease, expressed as percent reduction ofdisease, is included in Table III under the title "BRE 1000."

EXAMPLE 14 Control of Peanut Cercopsora Leafspot by Foliar Treatment

Four Virginia peanut plants were grown in each of a plurality of pots.Enough pots were prepared so that the four plants in each of the potscould be sprayed with each of the compounds listed in Table I. Thisspraying occurred when the plants reached 4 weeks old. The 48 compoundsof this invention were applied to the peanut plants by spraying emulsioncompositions, prepared in accordance with the method employed in Example9, in accordance with the method used in Example 10. The concentrationof the emulsion compositions were 900 mg/l for each of the compoundslisted in Table I. A number of pots containing four 4-week old Virginiapeanut plants were left untreated to act as controls.

The treated (sprayed) and control (unsprayed) plants, after drying, wereinoculated with spores of Peanut Cercospora leafspot, Cercosporaarachidicola. The inoculum contained 20,000 to 30,000 spores per ml. Theinoculum was sprayed with 1 to 2 drops of Tween [trademark] 20surfactant (ethoxylated sorbitan monolaurate) to aid in wetting theleaves with the inoculum. All the inoculated peanut plant pots wereincubated in a temperature-humidity control chamber at 24° C. for 36hours to develop infection. The plants were than placed in a greenhousefor 21 days to allow disease development.

After 21 days in the greenhouse, all the plants were evaluated on the 0to 6 disease rating system. Percent control was computed by comparingthe scores of the treated pots and the untreated control pots. Theresults of this test are summarized in Table III under the title "PNT900."

EXAMPLE 15 Control of Barley Blast

Pots were prepared such that they included 10 plants of 6 day old barley"Herta" variety. These pots were sprayed with compositions, formulatedin accordance with the procedure of Example 9, of the compounds setforth in Table I. These pots, and a number of control pots planted with10 "Herta" variety barley plants which were unsprayed, were inoculatedwith spores of the blast fungus, Pyricularia oryzae. In that Pyriculariaoryzae is the same fungus utilized in Example 12, the method ifinoculation was in accordance with the description given in thatexample.

All the inoculated pots were placed in a greenhouse maintained at atemperature of 21° C. and a humidity of 99% for five days. At that time,the plants were evaluated using the 0 to 6 disease rating scale. Percentcontrol was computed by comparing the treatment scores of the treatedand untreated pots. The results of this test are included in Table IIIunder the title "BBL 1000."

EXAMPLE 16 Control of Nine Fungus Species

Compounds listed in Table I were solubilized in acetone at aconcentration of 500 mg/l. That is, solutions were made of the compoundsof the present invention such that there was 500 parts by weight ofactive compounds per million parts by volume of acetone. Filter paperdiscs, each 11 mm. diameter, were dipped in each of the test solutions.The discs were allowed to air dry to drive off the acetone solvent. Anumber of discs were untreated to provide controls.

The treated and untreated discs were then placed on agar plates and 8fungus species: Alternaria solani (ALT), Botrytis cinerea (BOT),Fusarium oxysporum (FUS), Helminthosporium maydis (HMAY), Phytophthorainfestans (PHY), Sclerotinia sclerotiorum (SCM) and Sclerotium rolfsii(SCO) were added to the center of each test disc in the form of aculture plug with the fungus mat in contact with the treated paper ofthe test disc. Two drops of a ninth fungi species, Cercosporaarachidicola (CER), were added as a spore suspension (20,000 spores/ml)to the chemically treated test disc, rather than a mycelial cultureplug. The plates were incubated at 29° C. in an oven and then the eightfungus species were evaluated by measuring the radius from the center ofthe fungus colony of the treated disc compared to the radius from thecenter of the fungus colony of the untreated discs.

Percent growth inhibition of each of the compounds tested was determinedas a function of the difference between the radii of the treated anduntreated discs for the eight fungus species.

In the case of the Cercospora arachidicola (CER) fungi, scoring was doneon a numerical bases as follows:

100=Complete inhibition of germination and growth.

80=Nearly complete inhibition but some growth.

50=Partial inhibition of growth or, early complete inhibition but latergrowth begins.

20=Some inhibition of growth, but not significant.

0=No inhibition of growth.

The results of all the above tests appear in Table III under the titles"ALT500, " "BOT 500," "FUS 500," "HMAY 500," "PHY 500," "CER 500," "SCM500" and "SCO 500."

    TABLE III      Percent Fungicidal Control Cpd. ALT 500 BBL 1000 BMS 250 BOT 500 BRE     1000 CER 500 CMS 250 FUS 500 HMAY 500 PHY 500 PMP 1000 PNT 900 RCB 1000     SCM 500 SCO 500 BMP 1000 No. (Ex 16) (Ex 15) (Ex 10) (Ex 16) (Ex 13) (Ex     16) (Ex 10) (Ex 16) (Ex 16) (Ex 16) (Ex 15) (Ex 14) (Ex 12) (Ex 16) (Ex     16) (Ex 11)        1 45 100 65 35 25 100 100 75 80 0 50 55 -- 20 0 --  2 0 50 0 0 0 0 50     0 15 0 0 -- -- 0 20 --  3 0 -- 15 10 0 0 100 50 40 55 75 -- -- 15 50 --     4 50 40 60 40 0 100 100 25 30 45 75 -- -- 0 0 70  5 0 25 0 0 0 0 0 0 0 0     0 -- -- 10 0 70  6 80 100 85 100 95 100 100 60 85 100 100 -- -- 35 -- 75      7 -- -- 100 -- -- -- 100 -- -- -- -- -- -- -- -- --  8 85 100 75 100 0     100 35 100 100 100 0 -- -- 0 75 90  9 100 100 15 100 0 100 35 100 100     100 0 -- -- 0 0 90 10 100 100 15 100 0 100 35 100 100 100 0 -- -- 40 50     85 11 50 80 0 60 0 50 0 100 100 100 0 -- -- 15 25 35 12 97 100 90 50 75     100 100 96 90 0 100 90 60 35 50 -- 13 65 100 70 80 75 100 100 80 85 100     100 -- -- 30 0 95 14 25 0 65 0 0 -- 50 0 0 10 0 -- -- 0 0 0 15 5 65 20 0     0 100 0 35 60 30 0 -- -- 0 0 35 16 0 25 0 0 0 0 0 0 0 0 0 -- -- 20 5 20     17 0 0 20 0 0 0 0 45 35 45 0 -- -- 5 55 -- 18 35 95 80 40 10 100 100 30     35 65 0 -- -- 35 20 95 19 0 0 0 0 -- 0 -- 35 75 50 0 -- -- 35 75 -- 20     25 0 0 25 0 0 80 10 75 100 100 -- -- 0 15 20 21 100 15 5 25 0 100 60 15     75 0 100 -- -- 0 0 40 22 0 0 0 0 0 0 0 0 0 20 0 -- -- -- -- 35 23 47 100     100 5 90 100 95 0 100 100 95 55 42 50 0 100 24 100 100 100 100 100 100     100 100 100 100 100 -- -- 90 65 100 25 100 100 100 100 100 100 100 90     100 100 100 -- -- 55 0 95 26 75 100 0 15 0 100 20 0 100 100 0 4 -- 0 0     100 27 100 91 50 100 75 100 50 100 100 100 85 70 90 40 0 100 28 40 100     15 10 0 0 100 50 40 55 75 -- -- 15 50 100 29 0 25 20 0 0 0 0 25 0 30 0     -- -- 0 0 35 30 100 15 0 100 0 100 0 85 0 100 40 -- -- 25 0 80 31 65 35     0 15 0 50 20 60 100 100 100 -- -- 0 0 80 32 100 100 0 70 75 100 100 100     100 100 85 -- -- 15 20 100 33 25 -- 20 0 0 0 0 35 15 50 0 -- 80 0 15 35     34 45 -- 90 0 90 0 90 35 45 90 100 -- 60 35 30 35 35 15 0 100 25 0 0 100     15 65 55 50 -- -- 0 0 0 36 100 100 20 100 60 100 20 100 100 100 0 -- 0     20 0 100 37 10 60 65 0 0 0 75 10 65 15 0 -- -- 0 10 35 38 35 80 0 10 0     50 40 25 85 50 0 -- -- 0 0 65 39 75 20 0 75 0 100 0 70 100 100 0 -- -- 0     0 -- 40 0 15 60 0 0 0 60 0 0 15 0 -- -- 0 0 80 41 60 100 100 0 100 100     100 60 100 100 60 -- -- 0 0 100 42 100 -- 80 100 100 100 15 100 100 100     100 -- 100 0 0 100 43 100 -- 40 100 100 100 15 100 100 100 100 -- 100 70     25 100 44 100 -- 80 100 100 100 65 100 100 100 100 -- 100 40 0 100 45 20     -- 60 0 75 0 40 50 60 75 60 -- 100 0 0 85 46 0 -- 60 0 90 0 80 0 40 10     100 -- 80 0 0 50 47 35 -- 90 50 0 100 80 50 75 50 25 -- 0 0 0 75 48 0 --     65 50 0 0 15 40 35 35 0 -- 85 0 0 50

EXAMPLE 17 Growth Regulation of Soybean, Cotton, Bean and Barley Plants

Aqueous compositions of Compound Nos. 1, 3, 4, 6, 7, 9, 10, 12, 13,18-25, 27, 28, 30, 31, 35, 41, 44, 45, 47 and 48 were prepared inaccordance with the procedure set forth in Example 9. In particular,these compositions were prepared in concentrations of 1,000 mg/l and3,000 mg/l from 450 mg. of the compound dissolved or dispersed in 10 ml.distilled water or an organic solvent, usually acetone, to which 20 mg.of an emulsifying agent, usually ethoxylated sorbitan monolaurate (Tween[trademark] 20), was added. The solution or dispersion was diluted to150 ml. with distilled water, producing a 3,000 mg/l aqueouscomposition. By appropriate further dilution with distilled water, a1,000 mg/l aqueous composition was prepared.

The compositions, prepared in accordance with the above procedure, wereatomized with a DeVilbiss [trademark] No. 152 sprayer onto the foliageof soybean plants (Glycine max (L.) Merr. cv. Williams, 2 weeks old),cotton plants (Gossypium hirsutum L. cv. Stoneville 213, 3 to 4 weeksold), bean plants (Phaseolus vulgaris L. cv. Pinto III, 2 weeks old) andbarley plants (Hordeum vulgare L. cv. Herta, 1 week old). Sprayingcontinued until the foliage was wetted to the drip point. After 1 to 3weeks, depending on the plant species, the plants were evaluated forretardation of vegetative growth as against untreated controls.

The results of this plant growth test, in which the soybean, cotton andbarley plants were treated with 3,000 mg/l of the tested compounds andthe bean plants were treated with the same compounds at a concentrationof 1,000 mg/l, are summarized in Table IV.

                  TABLE IV                                                        ______________________________________                                        Percent Growth Retardation                                                    Cpd.  Bean      Barley      Cotton  Soybean                                   No.   (1000 mg/l)                                                                             (3000 mg/l) (3000 mg/l)                                                                           (3000 mg/l)                               ______________________________________                                         1     0        0           95      100                                        3    30        0           20      20                                         4    40        0            0      90                                         6    95        0           50      90                                         7    80        0           90      100                                        9    40        0            0      90                                        10    60        0           20       0                                        12    100       0           90      100                                       13    95        0           20      30                                        18     0        0            0      95                                        19     0        0           100      0                                        20    50        0           30      100                                       21    50        0           40      50                                        23    75        0           40      100                                       24    30        0           30      100                                       25    80        0           80      95                                        27    50        0            0      20                                        28    20        0            0       0                                        30     0        0           NT      30                                        31     0        0           NT      50                                        35    60        0           100     100                                       41    90        0           NT       0                                        44    50        0           NT       0                                        45    50        0           NT       0                                        47     0        0           NT      30                                        48    20        0           NT       0                                        ______________________________________                                         NT = Not Tested                                                          

The above embodiments and examples are given to illustrate the scope andspirit of the instant invention. These embodiments and example will makeapparent, to those skilled in the art, other embodiments and examples.These other embodiments and examples are within the contemplation of thepresent invention. Therefore, this invention should be limited only bythe appended claims.

What is claimed is:
 1. A compound having the structural formula##STR14## where R is C₂ -C₈ alkylene having 2 to 4 carbon atoms linkingX and Y;R¹ is C₁ -C₈ linear or branched alkylene; R² and R³ are the sameor different and are hydrogen, halogen, C₁ -C₈ alkyl, C₁ -C₆ alkoxy, C₁-C₆ alkylthio, C₁ -C₆ alkylsulfonyl, phenyl, phenoxy, cyano, nitro,--OCOR⁴, --COOR₅, --CH_(m) Q_(3-m) or --OCH_(m) Q_(3-m) ; R⁴ is C₁ -C₄alkyl; R⁵ is hydrogen or C₁ -C₄ alkyl; Q is halogen; X and Y are thesame or different and are oxygen, sulfur, sulfinyl, or sulfonyl; Z isCH; and m is 1, 2 or 3;or physiologically acceptable salts thereof.
 2. Acompound in accordance with claim 1 whereinR is --(CH)_(n) --, --CH₂CH(R⁶)-- or --CH(CH₃)CH(CH₃)--; R¹ is C₁ -C₃ alkylene; R² and R³ are thesame or different and are hydrogen, halogen, C₁ -C₄ alkyl, C₁ -C₄alkoxy, C₁ -C₄ alkylthio, C₁ -C₄ alkylsulfonyl, phenyl, phenoxy, cyanoor nitro; R⁶ is C₁ -C₆ alkyl; X and Y are the same or different and areoxygen, sulfur, sulfinyl, or sulfonyl; and n is 2 or 3;orphysiologically acceptable salts thereof.
 3. A process for controllingphytopathogenic fungi comprising applying a fungicidally effectiveamount of the compound of claim 1 to the locus under attack by saidfungi.
 4. A process for controlling phytopathogenic fungi comprisingapplying the compound of claim 1, at a concentration of 10 ppm to 500ppm, to the soil in which plants to be protected from phytopathogenicfungi are grown.
 5. A process for controlling phytopathogenic fungicomprising applying the compound of claim 1 as a coating to seeds ofplants to be protected from phytopathogenic fungi at a coatingconcentration of 5 to 75 grams of the compound of claim 1 per 100 kg. ofseed.
 6. A process for regulating plant growth comprising applying aplant growth regulant effective amount of the compound of claim 1 to theplant whose growth is to be regulated.
 7. A fungicidal compositioncomprising a fungicidally effective amount of the compound of claim 1and an inert carrier therefor.
 8. A plant growth regulant compositioncomprising a plant growth regulant effective amount of the compound ofclaim 1 and an inert carrier therefor.